Fluoran compounds

ABSTRACT

Novel fluoran compounds such as 2-bis-(5&#39;&#39;,6&#39;&#39;,7&#39;&#39;, 8&#39;&#39;-tetrahydro2&#39;&#39;-naphthylmethyl)amino-6-diethylaminofluoran and 2-(2&#39;&#39;thenylamino)-8-dimethylbenz(c)fluoran, which are useful as a coloring material for record material systems, such as pressuresensitive copying paper or heat-sensitive copying paper, wherein colored images formed by an electron-donor-acceptor color-forming reaction between coloring material and acidic material.

[ 1 Aug. 26, 197 5 221 Filed:

[ FLUORAN COMPOUNDS [75] Inventors: Koichi Koga, Toyonaka; Yukiaki Ito,Minoo, both of Japan [73] Assignee: Sumitomo Chemical Company,

Limited, Osaka, Japan Oct. 27, 1972 [21] Appl. No.: 301,490

[30] Foreign Application Priority Data Oct. 29. 1971 Japan 46-86643 Dec.27, 1971 Japan.... 46-1074 Feb. 10, 1972 Japan.... 47-14663 Feb. 24 1972Japan.... 47-19187 Apr. 13, 1972 Japan 47-37433 May 17, 1972 Japan47-49375 June 22, 1972 Japan 47-63031 July 17, 1972 Japan 47-71844 July17,1972 Japan 47-17845 July 28. 1972 Japan 47-76199 July 28. 1972 Japan47-76198 [52] US. Cl. 260/335; 117/362; 117/368;

260/240; 260/247.2 R; 260/268 PC; 260/293.58; 260/295 T; 260/304;260/306.8 R; 260/307 R; 260/307 D; 260/310 R; 260/326.l3 R; 260/326.36;260/330.5; 260/332.2 H

[51] Int. Cl. C07D 311/96 [58] Field of Search 260/335 [56] ReferencesCited UNITED STATES PATENTS 3,501,331 3/1970 Kimura et a1 260/335FORElGN PATENTS OR APPLICATIONS 4640.079 3/1971 Japan PrimaryExaminer-Norma 8. Milestone Attorney, Agent, or Firm-Stevens, Davis,Miller & Mosher [5 7 1 ABSTRACT Novel fluoran compounds such as2-bis-(5',6',7', 8'- tetrahydro-Z-naphthylmethyl)amino-6-diethylaminofluoran and 2-(2'-theny1amino)-8-dimethy1benz[c]fluoran,which are useful as a coloring material for record material systems,such as pressuresensitive copying paper or heat-sensitive copying paper,wherein colored images formed by an electrondonor-acceptor color-formingreaction between coloring material and acidic material.

3 Claims, No Drawings 1 FLUORAN COMPOUNDS In order to eliminate theinefficiencies and defects of a the oil carbon paper, pressure-sensitivecopying paper or noncarbon paper, which is economic and handy, hasrecently made its debut in place of the oil carbon paper complying withdemand for speed-up of office works.

Heretofore, leueoaurarnines, leucomethyleneblues, phthalides andfluorans are well known as color precursors. They are colorless ornearly colorless compounds, which may change to a certain coloringmatter when they are brought into contact with acidic electronacceptoras explained below.

For example, 2-methyl-6-diethylamino-fluoran having the followingformula is one of the well-known color precursors which are colorlesscompounds under ordinary condition but change to red coloring matters byopening their lactone ring when they are brought into contact withacidic electron-acceptor.

The pressure-sensitive copying paper is usually prepared by coating aback side of one sheet of paper with a color precursor such as aleucoauramine or a fluoran, and coating a surface of another sheet ofpaper with an acidic electron-acceptor substance such as kaolin,bentonitc, activated clay, acid clay, aluminum silicate, attapulgite,metal oxides, metal chlorides, metal sulfates, organic acids such asphenols, aliphatic acids or tannic acid, or phenolic resins such asp-phenylphenolformaldehyde resin, p-cyclohexylphenylformaldehyde resin,etc. The pressure-sensitive copying paper is used by placing the coatedpapers upon one another so that the back side of the first paper may befaced to the surface ofthe second paper, and the back side of the secondpaper to the surface of the third paper and so on. By applying pressureor impact to the papers by means of a pencil, a ball-point pen or atypewriter on the first paper, the material on the back side and theelectron accep'torsubstances on the surface of the papers are broughtinto contact with each other, whereby the colorless pressure-sensitivematerial moves to' the electron-acceptor layer and undergoes colordevelopment and therefore colored images can be obtained.

The aforesaid compound has defects that, when used as color precursorfor pressure-sensitive copying paper, it stains capsules in undesiredred color because it is slightly soluble in water or slightly acidic oralkaline water.

Further, it has a relatively high vapor pressure so that it tends tovaporize from the capsules to form ghost images which contaminateregular images on the pressure-sensitive copying paper and to cause theimages to disappear on the paper during storage for a long period oftime.

Thus, an object of the present invention is to provide a novelchromogenic material without aforesaid defects.

This object can be accomplished by providing a novel fluoran representedby the following formula (I), (ll), (lll), or (IV),

(II-I) wherein R, and R each represents hydrogen atom. a lower alkylgroup, a lower alkyl group substituted by halogen atom, lower alkoxygroup or hydroxyl group, benzyl group or a benzyl group substituted bylower alkvl group, lower alkoxy group, halogen atom or nitro group assubstituent R R represents a general formula.

R l H c 0 1 I l 085 R2 R4 provided that when R signifies I V C --(R A isnaphthalene l R nucleus is (fight S5 Q'- gln [Kg- 10M -CH2-CH=CHCOOR12 9n l0)n' N 414 -4 -13 (Rgl wm-U- (R l WW (R9),

wherein R R and R, each represents hydrogen atom, a lower alkyl group, ahalogen atom, a lower alkyl group substituted by halogen atom, loweralkoxy group or hydroxyl group, or phenyl group which may be substitutedby lower alkoxy group, lower alkyl group, halogen atom or nitro group; Rrepresents hydrogen atom, a lower alkyl group or an acyl group; R and Reach represents hydrogen atom or a lower alkyl group, R,, representshydrogen atom, a lower alkyl group or benzyl group; R,, and R eachrepresents hydrogen atom, a lower alkyl group, a lower alkoxy group,halogen atom, nitro group, amino group, an amino group substituted bylower alkyl group, lower alkoxy carbonyl group, a lower alkanesulfonylgroup or benzenesulfonyl group which may be substituted by at least oneRy, R represents a lower alkyl group, a halogenated lower alkyl group,an aralkyl group or an aralkyl group substituted by R,; R and R13represent hydrogen atom, a lower alkyl group, a halogenated lower alkylgroup, phenyl group, aralkyl group, or phenyl or aralkyl groupsubstituted by R.:' R represents hydrogen atom, a lower alkyl group,benzyl group or an acyl group; D represents a divalent radical, -O-, Sor (R has the above-defined meanings); W represents D or --CH,; Brepresents pyridine or quinoline nucleus; P represents direct bond, or adivalent radical,

formula,

@- (R9 in -cn -ca=cu Q R, represents R,,, or R,', R R, and R eachrepresents R R or R,,,; R, and R, each represents R phenyl group or aphenyl group substituted by R,; R (COL- OUR PRECURSOR NO. eachrepresents R,,, R, or R,,,; andR and R R, and R, and R, and R may form aring with a divalent radical, -(CH ),,W--'(CH CH2 C (R, is the same asdefined above), wherein q r is 3 or 4; W is the same as defined aboveprovided that W does not represent -CH in the case where A is benzenenucleus and q r= 4; n and n is an integer of l to 7; r is un integer ofl to 2; Y, represents hydrogen atom, a lower alkyl, a lower alkoxy, ahalogen atom such as fluorine, chlorine, bromine and iodine, aminogroup, or an amino group substituted by at least one lower alkyl groupor nitro group; 2 stands for hydrogen atom, a lower alkyl, halogen atomsuch as fluorine, chlorine,

bromine and iodine, lower alkoxy, nitro or amino group, or an aminogroup substituted by at least one lower alkyl groups, or groups of theformula,

(wherein R and R each represents hydrogen atom, a lower alkyl, phenyl,halophenyl, methoxyphenyl or nitrophenyl); m is an integer of l to 4; Arepresents benzene or naphthalene nucleus, and Y, signifies phenyl,cyclohexyl, or benzyl group.

Throughout the present specification, the term lower" as is seen in"lower alkyl group" indicates that the number of carbon atoms is from 1to 4.

Acyl group represents a group R'-CO in which R is an alkyl group havingl to 3 carbon atoms, or benzoyl group which may be substituted by analiphatic group having I to 4 carbon atoms or by R,.

The present invention has technical advance over prior arts in thefollowing points:

1. These fluoran compounds represented by the general formulas (l),(ll), (ill) and (IV) are colorless and stable in air at ordinarytemperature, but the compounds (I), (ll), ("1) and (IV) change in colorfrom white to red, green or black when they are brought into contactwith an acidic electron-acceptor explained above.

2. These fluoran compounds (I), (ll), (Ill) and (IV) show all sorts ofdark colors, for example, deep red, dark green, dark blue-green, darkgreenish black, or black according to the number, kind and position ofsubstituents.

It is also possible to use the said compounds together with other colorprecursors such as C.V.L. (crystal violet lactone), B.L.M.B. (benzoylleucomethylene-blue) or 2-tert-butyl-4-methyl-6-diethylaminofluoran,etc., to obtain a special color such as blue-black or black image on thepaper without spoiling the other color precursors. These are significantfeatures of the present invention.

3. These fluoran compounds are well soluble under colorless condition ina non-volatile non-polar solvent used for preparing a recording sheet.Examples of the non-polar solvent are as follows:

Cresylacetate, l-phenyl-3-methyl-indane, l,ldiphenylethane,bis-(a-methylbenzyl)benzenes; alkylated benzenes; alkylated naphthalenessuch as dimethylnaphthalenes anddipropylnaphthalenes; mineral oil;paraffin oil; olive oil; and tricresyl phosphate, etc.

Good solubility particularly in the aromatic solvents makes it easy toprepare the recording sheet and to obtain a deep image on the paper.

4. The present fluoran compounds have no solubility and good stabilityin water, acids or alkalis. For example, 2-(5f,6',7',8'-tetrahydro-2'-naphthylmethyl)amino-8-diethylamino-benz[clfluoran can be boiled with analkali solution without being destroycd.

5. The present fluoran compounds have good fast nesscs to light,moisture and sublimation.

The obtained deep image on this recording sheet does not disappear orchange in color by moisture or droplets of water, or by exposure tosun-light or by .heating.

The recording sheet prepared with use of the present fluoran compoundendures storage for a long period of time without the disappearance ofthe image on the documents and slips.

6. The present fluoran compounds have high colordeveloping speed. Suchcolor formation occurs just at once when the fluoran compounds in theform of crystals or a solution in the above-cited solvents are broughtinto contact with the acidic electron-acceptor. Then, the recordingsheet prepared with use of the present fluoran compounds gives vividdeep images on the paper at the moment when a pressure or impact isapplied onto the paper by means of a pencil, a ballpoint pen or atypewriter.

7. The images on the recording sheet prepared with a mixture of thepresent fluoran compounds do not change in color owing to the samecolor-developing speeds caused by the same fluoran nucleus. The presentfluoran compounds represented by the general formulas (I), (ll), (Ill)and (IV) may be prepared by the following methods.

In the presence of a dehydrating agent, fluorans (I), (II), (III) and(IV) can be prepared by reacting a o-(2'-hydroxyl-4'-aminobenzoyl)-benzoic acid represented by the formula,

m R N CO-Q COOH wherein R, and R signify R R,, R,., R,, R, and R,, Z andm are defined above, with a compound represented by the formulas R R ROR I! wherein R and R represent R R,,, R,, R,,, R and R,. E stands forbenzene, naphthalene or tetrahydronaphthalene nucleus. R" indicateshydrogen atom, a lower alkyl group or an acyl group, and R R, and Y areas defined above, to obtain a fluoran represented by the followingformulas,

9 R1 Y2 R O J /Rk 9 R wherein h RI! llh RIV! h h ks h Y1! Y2 M and E areas defined above.

The reaction may be effected at a temperatureof 0 to 300C for severalhours or sometimes for a few days in the presence of adehydrating-condensing agent. Examples of the dehydrating-condensingagent include sulfuric acid; phosphorous pentoxide; phosphoric acid;polyphosphoric acid; an hydrous metal halides such as anhydrous tinchloride or bromide, anhydrous zinc chloride or bromide, anhydrousaluminum chloride or bromide, anhydrous ferric chloride or bromide;phosphoric pentachloride or bromide; phosphorous trichloride or bromide;phosphorus oxychloride or oxybromide, and anhydrous hydrogen chloride orfluoride.

If necessary, carbon disulfide, chlorinated benzenes, or nitrobenzenesare used as a solvent for the reaction.

After. the reaction is over, the reaction mixture is poured into iceor'water to separate solid, and if desired, the mixture is neutralizedwith a solution of an alkali such as caustic soda, potassium hydroxidean the like.

in order to convert the resulting solid to the pure fluoran compoundrepresented by the formula (I), (ll), (Ill) or (IV) by purification, thesolid may be'dissolved and heated in a solvent and then the mixture maybe cooled or concentratedto obtain the fluoran compound (I), (ll), (lll)or (IV) as white crystals.

As a solvent for the purification, aromatic hydrocar bon solvents suchas benzene, xylene, etc.; nuclear halogenated aromatic hydrocarbonsolvents such as chlorobenzcne,v bromobenzene, dichlorobenzenes,trichlorobenzenes, etc.; alcohols such as methanol, ethanol, etc.; amidesolvents such as dimethylfonnamide,

halogenated aliphatic hydrocarbon solvents such as chloroform,bromoform,methylchloroform, etc.; and ethers such as dimethyl ether, diethylether, etc. are

useful. I i i a The purificationis often facilitated by the addition ofan aliphatic aminesuch as dimethylamine, trimethylamine, diethylamine,triethylamine, etc.; an aliphatic aminoalcohol such as ethanolamine,propanolamine, ctc.; or a heterocyclic'basic'substance such as pyridine,picolinc. ctc. 1 i

White crystals, which separate on heating and then cooling in any one ofthese purification solvents or a mixture thereof, are filtered andwashed with a'nonpolar solvent such as cyclohexane, nhexane, diethylether-to obtain a colorless compound. In case ofa com wherein R,,,, R YZ, E. and m are as defined above, may be reacted with a m-aminophenol ata proper reaction temperaturein the presence of a dehydrating agent asexplained above to obtain a fluoran compound.

The reaction preceeds as follows:

COOH

wherein R", R,, R R R Y., E, Z and m are as defined above. Thepurification procedure after the reaction is the same as that in thefirst method.

The third method is accomplished by the use of a fluoran compoundprepared by the first or second methods. Thus, a aminofluoranrepresented by the formulas,

, amino s'ubstituent of the fluoran nucleus, is treated with (whereinR,, R Rm, Rh, Y E, Z and m are as defined above), which has at least onehydrogen atom in the an alkylating agent,'an acylating agentorasulfonylating agent as explained below in the presence or absence of adehydrating agent or a dehydrohalogenating agent. The reaction isproperly carried out at 0 200C for (wherein R,, R R,, R Y., Z, m and Eare as defined several hours or sometimes for a few days, if desired,above, and X each signifys a residue of the alkylating, in the presenceof a solvent such as benzene, toluene, 3o acylating or sulfonylatingagent such as halogen atom, xylene, chloroform, l,2 dichloroethane,ether, dioxhydroxy group, 80,", POff', etc.)

ane, N,N-dimethylformamide, dimethylsulfoxide, alcoin the same way, afluoran compound represented by hols, etc. the formula (ill) may beobtained by reacting fluoran The reaction proceeds as follows: compoundrepresented by the formula,

N O 40 H/ W Rk U K R! gg co RIVX (wherein R., R,, R,,, R,, Y Z and m areas defined above), which has at least one hydrogen atom in the aminosubstituent, with an alkylating agent, an acylating agent or asulfonylating agent as explained below.

Examples of the acylating. alkylating and sulfonylati. Acetic anhydridePropionic anhydride Butyric anhydride Propionic anhydride Crotonicanhydride ing agents which may be used in the above-mentioned reactioninclude:

Benzoic anhydride l 3-Phenyl-2-propynyl bromide m-Chlorobenzoicanhydride 8. Oxiranes m-Nitrobenzoic anhydride Ethyleneoxidep-Bromobenzoic anhydride m-Methylbenzoic anhy- Propyleneoxide drideZ-Ethyloxirane p-Methoxybenzoic anhydride l5 2.2-Dimethyloxirane 2.Acetyl chloride Propionyl chloride 2,3-Dimethyloxirane2,2-Diethyl-3-methyloxirane Acryloyl chloride 2,2-DiphenyloxiraneMethacryloyl chloride 2-(4'-Nitrophenyl)-oxirane Acetyl bromide2-Phenyloxirane 2-(2'-Chlorophenyl)-oxirane Butyryl bromide t 9.Sulfonylating agents: Propiolyl bromide Methanesulfonyl chlorideCrotonyl bromide Ethanesulfonyl chloride Benzoyl chloridePropanesulfonyl chloride m-Chlorobcnzoyl chloride Butanesulfonylchloride p-Nitrobenzoyl chloride Benzenesulfonyl chloride m-Bromobenzoylchloride p-Toluenesulfonyl chloride p-Methylbenzoyl chloridem-Toluenesulfonyl chloride m-Methoxybenzoyl chloridep-Chlorobenzenesulfonyl chloride Benzoyl bromide lo-Chlorobenzenesulfonyl chloride m-Nitrobenzenesulfohyl chlorideo-Nitrobenzenesulfonyl chloride m-Methoxybenzenesulfonyl chloride andbromides thereof such as, for example,

Methanesulfonyl bromide Ethanesulfonyl bromide Benzenesulfonyl bromidep-Toluenesulfonyl bromide p-Chlorobenzenesulfonyl bromidep-Nitrobenzenesulfonyl bromide p-Methoxybenzenesulfonyl bromide 10.Miscellaneous p-Chlorobenzoyl bromide m-Nitrobenzoyl bromidem-Methylbenzoyl bromide -o-Methoxybenzoyl bromide- Also, as'thealkylating agent, the following compounds are preferable.

3. Esters: Dimethyl sulfate Diethyl sulfate Dipropyl sulfate Trimethylphosphate Triethyl phosphate Methyl benzenesulfonate Methylp-toluenesulfonate Propyl p-toluenesulfonate Methoxyethylp-toluenesulfonate Methoxypropyl p-toluenesulfonate Methylmethanesulfonate Propylmethanesulfonate 4. Lower alkyl halides: Methylchloride Ethyl bromide Propyl chloride c o 8 Butyl chloride 5. Benzylhalides: l 55 t 3 Benzyllchloride m-Nitrobenzyl chloride p-Chlorobenzylchloride m-Bromobenzyl chloride 6O p-Methylbenzyl chloridem-Methoxybenzyl chloride Bcnzyl bromide C p-Nitrobcnzyl bromide lo-Bromobcnzyl bromide C1-C3 m-Methylbenzyl bromide o-Methoxybenzylbromide 6. Allyl halides: C1Cl l2 Allyl chloride U men; s

CiCH B l0 CH3 Br I ClCH n:

chore-( 1 I t COCH;

no-cm gmcnym I Cl-CH QE m2 Q0 ClCHg -Q- ori -Q I l Compound Colourprecursor 1 ci-cs; Q-o-G a CI-CH As the dehydrohalogenating agent,

Sodium hydrogencarbonatze Potassium hydrogencarbonate Sodium carbonatePotassium carbonate Sodium acetate Potassium acetate and Caustic sodamay be used. Also if circumstances permit, the basic substance used inthe purification, may be used.

As the solvent in the third method, aromatic hydrocarbon solvents suchas benzene, xylene, etc.; halogenated aliphatic hydrocarbon solventssuch as chloroform, bromoform, methylchloroform, etc.; halogenatedaromatic hydrocarbon solvents such as chlorobenzene, bromobenzene,dichlorobenzenes, etc.; alcohol solvents such as methanol, ethanol,propanol, etc.', ether solvents such as diethyl ether, dimethyleneglycol, dimethyl ether, diethylene glycol, etc.; sulfoxide solvents suchas dimethyl sulfoxide, 'diethyl 'sulfoxide, etc.; and amide solventssuch as N,N'-dimethylformamide, dimethylacetamide, N-methylpyrrolidonemay be used.

Specific examples of the compounds of the general formulas (I), (ll),(Ill) and (lV) "produced by the above-mentioned methods according to thepresent invention which show excellent resistance to water, goodfastness to light and rapid color developing speed are as follows. Shadeon silica gel after development for eachcompound is also shown below.

Shade after development Dark green m.p. 242 244C Colour precursor 2H3CH2)2N Q Red N CH g m )2 m.p. 98.6 0

Colour precursor 3 on (orgcugyw o 3 CH Green 0 (1:0 as m.p. 136 140%Colour precursor 4 Colour precursor 5 (C2H5)2N Dark green m.p. 190 195oColour precursor 6 (CH3CH2)2N o D\ CH Dark green 0 3 60 org-@- 0@ mp.126,3c

Colour precursor 7 (CH3CH2)2N O Greenish black 0 K H 6O GHQ-G0 m. p.110.5%

Colour precursor 8 n e e r G Colour precursor 9 n e e r G m.p. 133 135CColour precursor 1O n e e r G Colour precursor 11 C O 6 9 1 8 T- .04 5.011 l MD- Pm 2 Colour precursor 12 Red m.p. 167 168C Colour precursor 13Dark green W 2 H C m.p. 196 198C 2 Colour precursor 14 C H N O 2 5 2Greenish black 0 NHCHTHSH m.p. 144 145C I C0 Colour precursor l5(CH3CH2)2N 0 Purplish black 0 NHCH 1 m.p. 213 2170 CO Colour precursorl6 Bluish green I m.p. 123 124o Colourrprecursor 1? (on on ocn Red c 2 232 co mp. 121.6C

Colour precursor 18 Green Colour preoursor 1g (CH3CH2)2N Green Colourprecursor 20 (CH3CH2)2N O 0 N(CH2CH2OCH3)2 Green Colour precursor 21Green Coloiuprecursor 23 (CH' CHQgN Dark green Colour precursor 24Relddish purple imp. 219.390

op. ,m. 242.1%

n w m m b .n n. m

d w m m R Red Colour precursor 26 Colour precursor 27 Colour precursor28 n on a u r r r G G .nuGUCHj Colour precursor 29 Colour. precursor '50Colour precursor 31 2-( I '-Naphthylmedryluminn)-8-dimethyl-uminobenzlclfluoran nrnyUurninn] Dark green Green Red Red

Red

Dark green Red I Red Dark green Red Red

Red

Green Green Dark green Blackish green Dark green Dark green Dark greenGreen Green Green Black-green Black-green Green Red Green GreenViolet-red BIaek-green Black-green Greenlah black Greenish blackGreenish black Green Berk-green Red Red

Green Red Green Red Red

-Continued diaflylaminobenzl clfluoran 2-[ 3'-( p-Methylphenyl)-propi0nyIamino]-8- Red bis(p-chlorobenzyl)aminobenzlclfluoran 2-(2'-Pyridylmethyl )amino-B-l bis- Green(melhoxymethyl)amino]-4'-2'.4'-dimelhylbenzylideneaminobenzl clfluoran2-l N-Ethyl-pyrrole-2'-carbonami-do]-8[ bis-(p- Redchlorobenzyl)amino]-4'-' dimethyluminobenzlclfluoran2-(4'-Methoxy-2-ethoxy-phenylamino)-8-di(3'- Redfurfuryhaminobenzlclfluornn 2-( 4'-Chlorobenzenesulfonylamino)-8-bis(S'- Red Greenish black Green Greenish black Greenish black 2-(2'-Furoylumino )-6-bis-( melhdxymethyl- Red )aminofluoran2-(u-Naphthylacetylamino )-6- Red dihenzylarninofluoran2-l3'-(4"-ChIoro-2"-methyIphenyI)-2'- Greenpropynyl]amino-6-bis-(B-chlorocthyhamino- Violet-black2-(p-Chl0roben7hydrylamino)-8- Dark green dielhylaminobcnzlclfluoran2-(o,pDichloro-p'-methoxybenzhydrylamino)- Green 8-dimelhylamin0fluoran2'(N.N-Bis-benzhydryl)amino-6- Red diethylaminofluoran 42-(N,N-Bis-benzhydryl)amino-8- Green 2-[ N-MethyHp-chlorobenzhydryhamino] Violet black Green-4-chloro-6-diethylaminofluorandiphenylelhyl)uminol-6-dimethylaminofluoran Green Red Red

Red

Red

Violet-red Violet-red Green Black-green -Continued Black-greenBlack-green Green Green Green Black-green Red Green Black-greenBlack-green Green Red Red Red Green Green Red Red

Red

Red

Red

Red

Black-green Green 7 Black-green -Continued benz!b1lhienylmethylaminol-8-din1ethylamino- 4'-methoxybenz!c lfluoran 4 ePentachlorophenyl\hio)benzyl-2"- Dark green Black green Dark greenBlack-green Dark green Dark green Dark green Red Red

Red

Red

Red

Red

Red

Red

Red

Green Red Red

Red

Red

Red

Red

Green Green Dark green Dark green Red Red

Green Green Green Green Red Red Red Red

-Cominued Z-Bia-(B-Methoxyethyl)umino-B-dibenzylumino- Green Green GreenGreen Red Red

Red

Green Red Green Green Green Reddish violet Black-green Green Red RedBlack-green Black-green Green Green Red Black-green Green Red Violet-redBlack-green Green Green Green Red Green Green Black-green Red r GreenRed Green Red Red 'Red Red

Green Blu ck green -Continued Green Red Black-green Green Black-greenRed Red

Red

Green Green Green Green Red Red

Red

Red

Green Red Green Green Red Red

Green 7 Dark green Green Green Dark green Green Red Green Green Red Red

-Continued 2-[ N-( 2'-thenyl)-p-toluenesulfonylumino1-6-bis- Red(o-bromobenzyl )aminofluoran 2-(N-2'-Quinolylmethyl-propionylsmino)-6-Red bisl rn-( n-propylbenzyl )aminol-fluorsn2-!a.a'-Diphenyl-phenethylamino]-6- Dark green methylaminofluoran 2-(l',l '-Diphenyl-n-butylsmino)4-n-buthoxy-6- Dark greendi-n-propylaminot'luoran 2-lN,N-Bis(2'-quinolylmethyl)smino]-8-bis(p-Red isopropylbenzyl)aminobenzlclfluorsn 2-1l-lsobutyl-l'-(a-nsphthyl)-n-propylamino]- GreenS-bis-lo-(n-butoxy)benzyl]aminobenzlclfluoran2-[4'-n-Butoxyearbonyl-Z'-thenylamino]-8- Greenbl|(-ymethoxypropyl)aminobenzlclfluoran M N-( 3'-Benzo[ blthlenyl)smino1-6-bis(7- Black-green hydroxy-n-propyl)sminofluorsn2-(2'-Furhrrylamino)-4-n-butoxy-6- Black-green diethylsminofluoran2-(N,N'-Di-2-thenylsmino)-4-methoxy 6- Dark green diethylaminofluoran i2-[N,N-bis-( 2'-pyrrolylmethyl )arnlno-6- Green diethylaminotluoran 12-[ 2'-Benzyl-4-methyl )cyclohexylaminol-S- Greendiethylaminobenzlcmuoran 2-l2'-(p-Methoxybenzyl)cyclohexylamino|-8-Green diethyluminobenzlclfluoran 2-l 2'-(p-Chlorobenzyl)cyclohexylaminol-S- Green diethylaminobenzlclfluoran2-(2,6'-Dibenzylcyclohexylamino)-6- Green diethylaminofluoran2-(2-Phenethylcyclohexylamino) 6- Green diethylaminofluorun 2-! 2'-('y-Phenylpropyl )cyclohexyiaminol-(r. Green diethylaminolluoran2-(2',6'-Diethylcyclohexylamino)-8- Green dibenz laminohenzlclfluoran2-l 2'- ethyl-6'-benzyl )cyclohexylamino1-8- Greendibenzylaminobenzlclfluoran 2-( l -Phcnethylethylamino)-8- Greendiethylaminobenzlclfluoran 2-(l' Green -Phenethylpropylamino)-8-diethylaminobenzlclfluoran 2-ll'-(p-Chloropheneth l)-2'- Greenmcthylpropylarninol-6 ibenzylarninofluoran 2-( l'-Phenethyl-Z'-methyl-propylamino)-8- Green dimethylaminobenzlclfluoran2-[ l'-(p-Methoxyphenethyl)pentylaminol-6- Green dimethylaminofluoran2-1 I '-Phenethyli'-methyl-butylamino]-8- Greendiethylaminobenzlclfluoran 2-( I '-(a-Methyl-p-methylphenethyl Greenpropylamino l-b-diethylaminofluoran 2-[ I'-(a-Methylphenethyl)butylaminol-b- Green dihenzylaminolluoran 2-[ l'-(a-Methylphenethyl )-2'- Green rnethylpropylaminol-8-dimethylaminobenzlclfluoran 2-[ l '-(a-Ethylphenethyl )butylamino 1-Green diethylaminobenzlclfluoran cording system utilizing an electrondonor-acceptor color-forming reaction between chromogenic material andacidic material. V

The pressure-sensitive recording systems generally comprisecolor-forming compounds on and/or withinone or more sheet supports, thecolor-forming compo-.

nents being isolated from one another by a pressurerupturablebarrierqwhere the color-forming compo nents are disposed on separatesheets as disclosed in U.S. Pat. No. 2,712,507, the record materialreferred to as a "transfer" or "couplet" system. in such system, asolution of a chromogenic material is held in rupturable microscopiccapsules coated onto one surface of a transfer sheet, while an adjacentreceiving sheet is sensitized with an acidic material. i.e., an electronacceptor. Most common acidic materials are activated acid clay and acidclays, such as attapulgite, zeolite, bentonite, kaolin and silica.Recently, monomeric phenols or acid reactant polymeric materials, suchas phenolic polymers, phenol acetylene polymers, maleic acid-rosinresins. have been suggested either alone or in combination with acidclays.

in the manufacturing method of such record material, for instance, anon-volatile oil containing a chromogenic material dissolved therein isprotected by encapsulation with coacerva'te film of a water-solublepolymer. The resulting coating composition containing dispersed capsulesare coated on one side of a sheet, and coating composition of saidelectron acceptors is coated on the other side of the sheet. Whenseveral sheets are laid one over another and impressed with a pencil orthe like. Capsules are collapsed torelease the oil containingchromogenic material which produces a duplicated image on contact with vthe electronacceptor. In another system as disclosed in U.S. Pat. No.2,730,457, a coating liquid containing both of the capsules chromogenicmaterial and acidic material is applied on one side of a sheet oralternatively, a coating containing capsules is first applied on oneside of a sheet and the second coating containing the electronacceptoris applied thereon. Thus, all the components are disposed on a singlesheet, the record material is referred to as self contained" system anddevelops image color where the pressure is applied.

As a modification of pressure-sensitive marking sys tem, Japanese Pat.No. 511,757 (corresponds to U.S. Pat. application Ser. No. 392,404,tiledon Aug. 27, 1964) discloses a recording; sheet, in which minute capsulescontaining liquid solvent are coated on one surface of a sheet supportand both of the chromogenic material and the acidic polymer are coatedon or impregnated in same sheet or other sheet in solid condition.

There is thermo-responsive record sheet as a markforming systemutilizing an electron donor-acceptor color-forming reaction. Forexample, Japanese Pat. Pub. No. l4039/ 1970 (corresponds to U.S. Pat.application Ser. No. 554,565 filed on June 1, 1966) discloses atemperature-responsive recordmaterial comprising a supporting sheetmaterial having crystal violet lactone and a phenolic material solid atroom temperature but capableof liquefying and/or vaporizing at normalthermographic temperatures, said lactone and phenolic material beingfurther capable of producing a mark-forming reaction upon reactivecontact.

The novel compounds of our invention are widely usedfor above-mentioned.mark-forming system as a colorless chromogenic compound, i.e., electrondonor,

EXAMPLEJ (COLOUR PRECURSOR NO. 24)

140 Grams'of 95 %-sulfuric acid-was eharged'into a four-necked flask. Amixture of 26.5 g of 2-hy'droxy-5- amino-diphenyl hydrochloride and31:3-g of "o-(-2'- hydroxy-4 -diethylaminobenzyl) benzoic acid was addedfor one hour below 25C: At that time, the'hydrogen chloride gas evolvedwas absorbed in a absorber. After dissolution, the mixture was warm edto 25 to 30C for 8 hours. After cooling, the reaction mixture was thenpoured into 1.5 kg of ice-water at 10 'to C.-The mixture was neutralizedwith an aqueous caustic soda solution at the'same temperature.

The precipitate was filtered and washed with water. The thus obtainedcrude solid, 2-amino-4-phenyl-6- dietjnylaminofluoran was dissolvedin500 g of benzene and 'dehydrated with 50 g of anhydrous sodium sulfate.After addition of 5 g of active charcoal, the benzenesolution wasfiltered while hot. The filtrate was concentrated under reduced pressureto obtain the syrups.

Thus, 2-amino-4-phenyl-6-diethylaminofluoran was obtained as whitecrystals. After recrystallization from benzene the compound Ihad m.p.of-2l9.-3C.

The resulting compound, formed dark reddish brown color on contactingwith silica gel when used as a material for pressure-sensitivecopyingpaper. The'image having excellent fastnesses to moisture, sublimationand alkali was produced.

EXAMPLE 2 (coLouR PRECURSOR No, 8)

By. use of the same procedure as in Examp1e:1,'2-( 1-pyrr'olidinyl)-6-diethylaminofluoran was prepared fromN-(4-hydroxyphenyl)-pyrro1idine and 2-(2'-hydroxy-4-diethylaminobenzoyl)-benzoic acid. Yield: 41.8 Meltingpoint: 238 240C.This compound formed dark'green color on silica gel withgood fastnessesto light and moisture.

EXAMPLE 3 (COLOUR PRECURSOR NO. l7)

According to the same method as in Example -1, 2-[N,N-bis-(B-methoxyeth'yl)aminol-8- sol,

36 diethylaminobenzlclfluoran was prepared from N,N-bis-(B-methoxyethyll-4-amino l naphthol and 2-(2'-hydroxy-4EdiethylaminobenzoylJ-benzoic acid. This derivative having amelting point'of l95.3 to 196.3C formed dark green color on silica gel.'

EXAMPLE 4 (COLOUR PRECURSOR No. 22

On cooling with, water-in 3 00 cc flask, 25.3 g of 4-cyclohexylamino-lnaphthol was dissolved in 150 g of sulfuric acid below 20C. Then at thesame temperaturc, 3l.3 g of 2-(4'diethylamino-Z'-hydroxybcnzoyl)-benzoic acid was added. After completionof the dissolution, the reaction mixture :was stirredfor 15 hoursbetween 20C and 30C. After the reaction was over, the reaction content.was poured into 1.5 kg of ice-water mixture at about 0C. Afterneutralized and set the pH to ll with sodiurn'hydroxide solution, theobtained crude solid was filtered, the solid was recrystallizedrepeatedly 26 g of 2 -cyclohexylami'no-8-diethylamino-benz[c]fluoran wasobtained as white crystals having a'melting point of 272.2C. Thiscompound formed dark green color on silica gel anddid not change incolor during storage for a long period of time.

EXAMPLE 5 (COLOUR PRECURSOR N0. 23)

In the same way colour precursor No. 23,, 2-cyclohexylamino--diethylaminofiuoran was obtained fromN-cyclohexyl-p-anisidine and 2-(4'-diethylamino2'-hydroxybenzoyl)-benzoic acid. This compound formed greenish blackcolour on silica gel andhad a good fastness to light and moisture. m.p.:212.2- 213.2C

EXAMPLE 6 (COLOUR PRECURSOR NO. 27)

Colour precursor No. 27, 2-amino-8-diethylamino-3,4,5,6-tetrahydro-benz[c]fiuoran was prepared with 4-amino5,6,7,8-tetrahydro-l naphthol and 2 -(4'-diethylamino-Z'-hydroxybenzoyl)-benzoic acid. This compound, having amelting point'of242. 1C gave reddish brown colour on silica gel.

EXAMPLE 7 (COLOUR PRECURSOR NO. 20)

2-[N,N-bis-lB-methoxyethyll aminolodiethylaminofluoran prepared fromN,N-bis-(B- "methoxyethyl)-p-anisidine was obtained as white crystals,mp; 953C. This derivative gave dark green colour on silica gel and goodlight fastness.

i EXAMPLE 8 1n the same manner as in Example 1, the following compoundswere synthesized. Shade on silica gel is shown on the right hand column.

Bunauy tbenzotc aetd Amtnophencl Colour Grunt" cmmtGcoQno bun HO O M-U11. Br

1. A COMPOUND OF THE FORMULA 2.2-(2''-Benzylcyclohexylamino)-8-diethylaminobenz(c)fluoran. 3.2-Cyclohexylamino-8-diethylaminobenz(c)fluoran.